Fluorinated polymeric paper sizes and soil-release agents

ABSTRACT

Novel fluorine-containing paper sizes which impart oil and grease resistance to paper and soil-release properties to textile products are described which are the copolymerization products of (a) a perfluoroalkyl-substituted (meth)acrylate or (meth)acrylamide, (b) a secondary- or tertiary-amino or quaternary ammonium group-containing (meth)acrylate or (meth)acrylamide, (c) vinylidene chloride and, optionally, d) other copolymerizable nonfluorinated vinyl monomers.

FIELD OF THE INVENTION

[0001] The present invention concerns novel internally or externallyapplied fluorine containing polymers which impart oil and greaseresistance to paper and soil-release properties to textile products.More particularly it concerns copolymerization products of (a) aperfluoroalkyl-substituted (meth)acrylate or (meth)acrylamide, (b) asecondary or, tertiary amino or quaternary ammonium group-containing(meth)acrylate or (meth)acrylamide and (c) vinylidene chloride and,optionally, d) other copolymerizable vinyl monomers, their preparationand use.

BACKGROUND OF THE INVENTION

[0002] The use of perfluoroalkyl-substituted compounds to impart oil andgrease repellency to textile and paper substrates is along establishedpractice. For paper treatment the most important products havetraditionally been phosphate diesters of a perfluoroalkylalkanol ordi-perfluoroalkyl-substituted carboxylic acids, as described in U.S.Pat. Nos. 4,485,251, 4,898,981 and 5,491,261. These compounds areapplied either in the wet-end—that is they are added to the pulp—orapplied by rollers, a size press or other means to the finished paper asa coating. The fluorochemicals used for treating textiles are allpolymers; the vast majority are copolymers of poly-perfluoroalkyl(meth)acrylates. More recently such polymers have also been used asexternal paper sizes since polymers provide the extra benefit of waterresistance which is a desirable feature in many food packaging andfast-food applications.

[0003] To achieve water repellency by internal sizing,alkyl-ketene-dimer (AKD; sold under the trade name HERCON by HerculesInc., among others) is most commonly used since the small amount offluorine add-on (typically 0.08-0.12%) is inadequate for this purpose.In addition, the commonly used internal fluorochemical oil-sizingagents, even while impart oil sizing, have, due to their inherentlysurfactant-like “head-tail” structure, a deleterious effect on waterresistance by inhibiting the AKD curing reaction.

[0004] The present invention concerns fluorochemical polymers which areuseful as an internally or externally applied oil- and grease proofingpaper size which imparts, in addition to oil resistance, excellent waterresistance. It has further been discovered that the polymers of thepresent invention impart excellent soil-release and anti-soilingproperties to textiles.

[0005] The polymer of the present invention is a copolymer of

[0006] a) 45-90% by weight of a perfluoroalkyl-substituted(meth)acrylate or acrylamide,

[0007] b) 5-30% by weight of a secondary or tertiary amino or quaternaryammonium group-containing (meth)acrylate or (meth)acrylamide,

[0008] c) 1-20% by weight of vinylidene chloride (VDC), and, optionally,

[0009] d) 0-10% by weight of a nonfluorinated vinyl monomer.

[0010] Relevant prior art includes U.S. Pat. No. 3,919,183 (Jager etal.), which discloses polymers useful as oil repellent coatings forporous substrates such as textile materials and paper which comprise aperfluoroalkylethyl acrylate, optionally copolymerized with up to 95% byweight of other monomers. Among other possible co-monomers, vinylidenechloride and N,N-dialkyl-aminoethyl methacrylate are mentioned. Howeverno vinylidene chloride-containing compositions are exemplified.

[0011] U.S. Pat. No. 4,013,627 (Temple) describes textile finishes whichare copolymers of 20-99% by weight of a perfluoroalkylethyl acrylate,1-80% of a vinyl monomer having no non-vinylic fluorine atoms and 0.1-4%of a (meth)acrylate bearing a quarternary ammonium group. Among thepossible co-monomers, vinylidene chloride is mentioned but not employed.

[0012] U.S. Pat. No. 4,100,340 (Waldmann et al.) describes textilefinishes which are copolymers of a perfluoroalkylethyl acrylate, ahigher alkyl acrylate, vinylidene chloride and acroylbutylurethane inweight ratios of 1/0.22-0.39/0.45-0.85/0.01-0.14.

[0013] U.S. Pat. No. 4,582,882 (Lynn et al.) describes fluorinated papersizes which are copolymers of 60-80% by weight of a perfluoroalkylalkylacrylate; 1-30% of a halogenated alkyl or alkoxyalkyl acrylate, 1-15% ofglycidyl methacrylate, 1-6% of a (meth)acrylate bearing a quaternaryammonium group and 0-20% vinylidene chloride.

[0014] U.S. Pat. No. 4,742,140 (Greenwood et al.) describes copolymersfor use on textiles which comprise 40-75% by weight of aperfluoroalkylethyl acrylate, 10-35% of vinylidene chloride and 10-25%of a C₂-C₁₈alkyl-(meth)acrylate. An earlier Japanese Patent ApplicationNo. 50-54729 (Asahi Glass Co.) discloses similar polymers, but specifies35-60% of vinylidene chloride and 0.5-5% of N-methylol (meth)acrylamide.

[0015] It has now been unexpectedly found that copolymers comprising aperfluoroalkylalkyl (meth)acrylate, a secondary- ortertiary-aminoalkyl(meth)acrylate, vinylidene chloride and up to 10% ofcopolymerizable nonfluorinated vinyl monomers give superior oil andwater resistance to paper products, especially when applied as internalsizes. None of the cited prior art discloses the use of vinylidenechloride and a secondary- or tertiary-aminoalkyl(meth)acrylate as solecomonomers with a perfluoroalkylalkyl (meth)acrylate.

[0016] It has further been discovered that the copolymers of the presentinvention impart excellent soil-release and anti-soiling properties totextile fibers.

DETAILED DISCLOSURE

[0017] The present invention concerns compounds which act either asinternally or externally applied oil- and grease proofing paper sizes oras soil-release agents for textile fibers. The preferred compounds arecopolymers comprising monomers copolymerized in the followingpercentages by weight, relative to the total weight of the copolymers:

[0018] a) 45-90% by weight of a monomer of formula

R_(F)—W—X—C(═O)—C(R₁)═CH₂   (1),

[0019] wherein

[0020] R_(F) is a straight or branched-chain perfluoroalkyl groupcontaining 4 to 20 carbon atoms,

[0021] R₁ is H or CH₃,

[0022] X is O, S or N(R₂), wherein R₂ is H or an alkyl group with 1 to 4carbon atoms,

[0023] W is alkylene with 1 to 15 carbon atoms, hydroxyalkylene with 3to 15 carbon atoms, -(C_(n)H_(2n))(O C_(m)H_(2m))_(q)-,—SO₂NR₂-(C_(n)H_(2n))- or —CONR₂-(C_(n)H_(2n))-, wherein n is 1 to 12, mis 2 to 4,

[0024] q is 1 to 10 and R₂ is as defined above;

[0025] b) 5-30% by weight of a monomer of formula

(R₂)₂N—(CH₂)_(k)—X₁—C(═O)—C(R₁)═CH₂   (2),

[0026] in which the nitrogen atom is partially or completely quaternizedor in the form of a salt and

[0027] X₁ is O or N(R₂) and wherein

[0028] R₁ and R₂ are defined as above, each R₂ is the same or different,and

[0029] k is 2 to 4;

[0030] c) 1-20% by weight of vinylidene chloride, and, optionally,

[0031] d) 0-10% by weight of a copolymerizable nonfluorinated vinylmonomer.

[0032] Preferably d) is zero.

[0033] Especially referred are copolymers in which the monomers arecopolymerized in the following percentages by weight, relative to thetotal weight of the copolymers: a), 70-85% by weight; b), 3-12% byweight; c), 10-20% by weight, and d), zero.

[0034] In preferred copolymers, R_(F) is a straight chain perfluoroalkylgroup with 6-16 carbon atoms, X and X₁ are oxygen and W is an alkylenewith 1 to 12 carbon atoms, or X is N(R₂), X₁ is oxygen and W is—SO₂NR₂-(C_(n)H_(2n))-, wherein R₂ and n are as defined above.

[0035] The most preferred copolymers are those in which R_(F) is astraight chain perfluoroalkyl group with 6 to 16 carbon atoms, R₁ ishydrogen, X and X₁ are oxygen and W is —CH₂CH₂—.

[0036] A mixture of compounds of the formula (1) with 6 to 16 carbonatoms is advantageously employed to prepare the inventive copolymers.The most especially preferred monomer of the formula (1) to prepare thepolymers of this invention is an R_(F)-ethyl acrylate which is availablefrom Clariant Chemical Corp. under the trade name FLOWET AC-812. It hasa chain-length distribution of R_(F)-chains of 13±2% C₆F₁₃, 48±2% C₈F₁₇,23±2% C₁₀F₂₁ and 1.6% C₁₂F₂₅ or higher.

[0037] Preferred compounds of the formula (2) are N,N-dimethylaminoethyl(meth)acrylate; N,N-diethylaminoethyl (meth)acrylate;N,N-dimethylaminopropyl methacrylamide and N-tert. butylaminoethylmethacrylate and their salts.

[0038] Useful as co-monomers (d) are a large number of commerciallyavailable acrylates and methacrylates, as well as styrene; butpreferably methyl methacrylate, N-methylol acrylamide, 2-hydroxyethylmethacrylate, acrylic acid, glycidyl methacrylate and acrylonitrile.

[0039] The polymerization of the monomers to form the copolymers of theinvention can be carried out as an emulsion or in solution. For emulsionpolymerization water-soluble co-solvents are commonly used to aidmigration of the otherwise insoluble R_(F)-monomers through the aqueousphase. Useful co-solvents include acetone and methanol. Suitable freeradical initiators include water-soluble peroxides or azo compounds,such as potassium persulfate. In another variation of the polymerizationin an aqueous medium, the R_(F)-monomer is first emulsified in waterusing a surfactant and a homogenizer, followed by copolymerization withthe other monomers.

[0040] The preferred method for making the polymers of this inventionhowever is solution polymerization. Useful solvents are ketones such asacetone, methyl isobutyl ketone and methyl ethyl ketone, esters such asisopropyl acetate, alcohols such as methanol, ethanol and isopropanol,and aromatic hydrocarbons such as toluene.

[0041] The polymerization is typically carried out at temperatures offrom about 50 to 100° C. using a free radical initiator, typically aperoxide or azo compound. Useful initiators include benzoyl peroxide,1,2-azo-bis-isobutyronitrile (AIBN) and 1,2-azo-bis-(2-methylbutanenitrile) (VAZO-67).

[0042] A chain-transfer agent can be present, such as an alkyl thiol, inamounts of from 0.01 to 1 mole percent. After the polymerization iscomplete, the solution is readily transformed into a cationic aqueousemulsion or solution by first adding an organic acid such as acetic acidand water; then distilling off the solvent.

[0043] The copolymers are useful as coatings on porous substrates suchas paper and textiles, or on hard substrates such as wood, metal ormasonry. In the paper industry, their main usefulness is based on theirability to impart oil and grease resistance to paper which is used forfood packaging or for any other type of application where resistance tooily substances is required.

[0044] Thus the present invention further relates to a method ofimparting oil and grease resistance to paper, which comprisesincorporating an amount of a copolymer according to this invention thatis effective to impart oil and grease resistance into the paper.

[0045] The application of the copolymer to paper can either be to thedry paper through a coating process via a size-press (external papersizing) or by addition of the copolymer to an aqueous pulp (internalpaper sizing). The level of application in either case is preferably inthe range of 0.02 to 1% by weight of the copolymer, based on the weightof the dry paper or pulp, corresponding roughly to incorporation of 0.01to 0.5% by weight of fluorine on the paper or pulp.

[0046] The usefulness of the copolymers for treating textile materialslies in their ability to impart soil release characteristics to a fabricduring washing, thus facilitating the removal of stains fromtablecloths, pants, shirts, etc., thereby extending their useful life,and to enhance the ability of the treated textile material to shed drysoil. The term soil-release denotes the ease with which a fabric, oncestained or soiled, can be washed clean. The anti-soiling effectdescribes resistance to picking up of dry soil and wet soil (=soilredeposition) by the treated textile material. A soil-release finish isusually a fluorochemical hydrophilic polymer, where the fluorochemicalsegment provides stain repellency and the hydrophilic segment provideswettability and washability.

[0047] Suitable textile materials include cellulosics, especiallycotton, polyamides such as nylon, wool and silk, polyesters andpolyolefins and blends thereof such as polyester-cotton blends.

[0048] Thus the present invention further relates to a method to impartsoil-release and anti-soiling characteristics to a textile material,which comprises treating the textile material with an amount of acopolymer according to this invention that is effective to impartsoil-release and anti-soiling characteristics thereto.

[0049] The preferred amounts of the copolymer to treat the textilematerial with are the same as for paper or pulp.

[0050] The present invention further relates to textile material orpaper or pulp which contains 0.02 to 1% by weight of a copolymeraccording to claim 1 therein.

[0051] The following non-limiting examples disclose how to synthesizethe inventive copolymers and describe in detail methods of theirapplication to various substrates. They also demonstrate the goodperformance of the copolymers on the various substrates.

EXAMPLE 1

[0052] An autoclave fitted with a magnetic coupled agitator is chargedwith 240.0 g of a perfluoroalkyl-ethyl acrylate with a homologuedistribution of R_(F)— chains of 13±2% C₆F₁₃, 48±2% C₈F₁₇, 23±2% C₁₀F₂₁and 1.6% C₁₂F₂₅ or higher (FLOWET AC 812 from Clariant); 40.0 g ofN,N-dimethylaminoethyl acrylate (DMEA) and 200.0 g of methyl isobutylketone. The autoclave is subjected to reduced pressure and released withnitrogen. To the autoclave 15.0 g of vinylidene chloride and 0.8 g ofazobisisobutyronitrile are charged. The polymerization is performed at66° C. for 20 hours, during which the pressure goes to 0.2 bar. To thepolymerization mixture at 60° C. a mixture of water (450.0 g) and aceticacid (30.0 g) is added. This is stirred for 15 min. The polymerizationmixture is collected into a roundbottomed flask and methyl isobutylketone is removed under vacuum to give 580.0 g of copolymer solution.

EXAMPLES 2 to 7

[0053] The procedure of Example 1 is used to prepare Examples 2 to 6,using the comonomer weight ratios listed below.

[0054] The copolymer of Example 2 precipitated out in water and aceticacid due to the reduced amount of N,N-dimethylaminoethylacrylate.Composition of Copolymers, in weight percent Amino (meth)- VinylideneEXAMPLE R_(F)-monomer acrylate Chloride Other 1 81 14 DMEA 5 — 2 80 10DMEA 10 — 3 75.5 14 DMEA 10.5 — 4 81.4 6.8 DMEA 5.1 6.8 DMPM 5 81 14DMEM 5 — 6 81 13 DMEA 5 1 HEMA 7 81 14 DEEM 5 —

EXAMPLE 8

[0055] The procedure of Example 1 is repeated, using 2.4 g n-dodecylmercaptan as chain-transfer agent.

[0056] The following examples describe the synthesis of comparativepolymers without VDC.

EXAMPLE 9

[0057] A flask fitted with a reflux condenser and stirrer is chargedwith 20.0 g perfluoroalkylethyl acrylate with a homologue distributionof R_(F)— chains of 13±2% C₆F₁₃, 48±2% C₈F₁₇, 23±2% C₁₀F₂₁ and 1.6%C₁₂F₂₅ or higher (FLOWET AC 812 from Clariant); 2.5 g ofN,N-diethylamino-ethyl methacrylate; 1.0 g of N,N dimethylacrylamide and15.0 g of methyl isobutyl ketone. The charge is purged with nitrogen at40° C. To the flask 0.04 g of azobisisobutyronitrile is added. Thepolymerization mixture is held between 60 and 65° C. for 20 hours. Tothe polymerization mixture another 0.03 g of azobisisobuyronitrile isadded. The mixture is stirred at 65° C. for an additional 3 hours. Tothe polymerization mixture at 60° C. a mixture of water (100.0 g) andacetic acid (1.4 g) is added. This mixture is stirred for 15 minutes.The polymerization mixture is collected into a round bottom flask andmethyl isobutyl ketone is removed under vacuum to give 120.0 g ofcopolymer solution (20% solids).

EXAMPLES 10-12

[0058] Following the procedure of example 9, polymers with thecompositions listed in the following table were synthesized. Compositionof Copolymers, in weight % Flowet Amino EXAMPLE 812 (meth)acrylate Other9 85 11 DEEM 4 DMA 10 78 13 DEEM 7 MMA 2 GMA 11 83 15 DEEM 2 GMA 12 83.514.5 t-BEM 2 GMA

[0059] The following example shows the performance of the novelR_(F)-polymers as internal paper sizes.

EXAMPLE 13

[0060] The compounds of Examples 1-12 were tested as described below.

[0061] Internal Size Application and Testing:

[0062] Paper plates of 10 inch diameter were made on a small scale paperplate-making machine, supplied by the CHINET Company. This machineconsists of a rotating element bearing three radially attached dies, onecalled the “forming die” which in step 1 is immersed in the pulp andthrough which the pulp is filtered onto the plate by vacuum; after a ¼revolution the plate reaches step 2, a die called the “vacuum die” whichmolds and dries the plate by suction and heat, and in two more ¼revolutions reaches two more cross-head dies which further dry the plateby heat. The final dryness of the plate is influenced by the strength ofthe vacuum and the drainage characteristics of the pulp, and by thetemperatures of the various dies. A minimum dryness of at least 94%(i.e. 6% water or less) is desirable, otherwise the paper plates loosewet strength.

[0063] In the following experiments these conditions were used:

[0064] Machine Settings: 10 inch plates;

[0065] Target dryness: 95-96%; vacuum die: 300° F./1.XH: 385° F./2.XH:375 F.

[0066] Wet End:

[0067] Pulp supplied by the CHINET Company, 3 pounds/trial run,containing as wet-end chemicals, added in 40 sec intervals to thestirred pulp, in order of addition:

[0068] Nalco 7607—cationic retention aid and coagualant (NALCOCHEM.Co.), 8 pounds/ton;

[0069] Alkyl-ketene dimer (AKD) Water repellent (HERCULES Corp.), 6pounds/ton

[0070] the fluorochemical polymeric size: calculated to give 0.1% Faddon;

[0071] Nalco 625—anionic coagulant (NALCO CHEM CO.), 1 pound/ton.

[0072] Tests: two tests were carried out:

[0073] Hot Saline Solution and Hot Oil test:

[0074] Procedure:

[0075] 1. weigh paper plate.

[0076] 2. pour either 2% saline at 72° C. or Mazola oil at 99° C. ontoplate, enough to fully cover surface.

[0077] 3. after 5 minutes, pour off solution, wipe plate dry with papertowels and reweigh.

[0078] 4. calculate % absorption and rate visually the degree ofpenetration (R): R=0=>50%; 1=25-50%; 2=<25%; 3=none.

[0079] Percent absorption is the more accurate measure of water/oilholdout performance.

[0080] The finished plates were tested “off machine”, i.e. shortly aftermade and after 24 hours. Plate dryness “off-machine” was determinedgravimetrically.

[0081] The test results are shown in the following table. Hot WaterHold-Out Cpd. Hot Oil (2% Saline) of Ex. % F % Hold-Out off machine 24hrs. No. VDC added dryness R % abs R % abs R % abs 1 yes 0.09 96 3 7 2-315 3 14 2 yes 0.09 96 1-3 21 2-3 15 3 14 3 yes 0.08 96 1-2 20 2 17 3 134 yes 0.08 96 1-2 23 2 14 3 12 5 yes 0.10 96 0 31 2 20 3 12 6 yes 0.1096 3 5 2 30 3 11 7 yes 0.12 95 2-3 15 2-3 14 3 15 8 yes 0.10 96 3 6 1-242 3 13 9 no 0.09 96 0 32 2 16 3 13 10 no 0.09 95 0 38 2 13 3 14 11 no0.10 95 0 39 1 22 3 12 12 no 0.10 97 0 32 2 21 3 12

[0082] The results demonstrate the superior oil hold-out performance ofvinylidene chloride-containing copolymers, especially those of examples1, 6 and 8, versus non-vinylidene chloride-containing copolymers ofexamples 9-12.

EXAMPLE 14

[0083] The following example shows the usefulness of the novelcopolymers as external paper sizes.

[0084] External Size Application:

[0085] The neutralized test solutions are added to a 4% aqueous solutionof paper makers starch (Stayco M, oxidized starch, from Staley Corp.)and then applied to unsized paper by padding (paper dipped throughstarch solution, and passed through single nip rollers). The resultingsheets are dried at ambient conditions for 15 minutes, then 3 minutes at200° F. (97° C.) in an “Emerson Speed Drier” (heated metal plate withcanvas cover).

[0086] Oil and Grease Resistance Tests:

[0087] Oil Kit Test:

[0088] The oil repellency of the surface is determined by using theTAPPI UM 557 OIL KIT TEST, which consists of determining with which oftwelve castor oil-heptane-toluene mixtures having decreasing surfacetension penetration occurs within 15 seconds; ratings go from 1, lowest,up to 12.

[0089] Ralston-Purina (RP2) Test:

[0090] Grease resistance is determined with the Ralston-Purina test forpet food materials; RP-2 Test, Ralston-Purina Company, PackagingReference Manual Volume 06, Test Methods. In summary: cross-wise creasedtest papers are placed over a grid sheet imprinted with 100 squares.Five grams of sand are placed in the center of the crease. A mixture ofsynthetic oil and a dye for visualization is pipetted onto the sand andthe samples are maintained at 60° C. for 24 hours. Ratings aredetermined by the percentage of stained grid segments, using at leasttwo samples.

[0091] Turpentine Test, according to TAPPI T454 om-94, a preliminarytest to determine rates at which oil or grease can be expected topenetrate the paper.

[0092] Water and Alcohol Resistance Tests

[0093] Cobb Size Test:

[0094] Water resistance is determined using the Cobb Sizing test, asdescribed in TAPPI T 441 om-90.

[0095] IPA Resistance Test:

[0096] In this test drops of isopropanol—water mixtures are placed onthe paper and after 3 minutes the under side of the paper is monitoredfor penetration; if no penetration has occurred, a mixture with the nexthigher IPA content is applied. The rating is based on the highest % byweight IPA which does not penetrate. Ratings are based on 5% IPAincrements.

[0097] Pet Food—“Felix” Test:

[0098] This is a very stringent test, carried out under conditions ofhigh humidity and heat. French “Felix” brand cat food is placed as a 2cm thick layer on 100 cm² of the treated paper; this sample is then putunder a weight of 7 kg and kept in an environmental chamber at 70° C.and 67% moisture for 16 hours. The paper is then visually inspected forsigns of fat penetration and the area percent of penetration iscalculated. The results are shown in the following table. Tur- Cobb IPAFelix Cpd. of Oil pentine Size Hold- Test Ex. No. VDC % F Kit RP-2 TestTest out Test Area % 1 yes 0.09 10 4 × 0 1800+ 23 40 15 6 yes 0.09 10 4× 0 1800+ 24 40 20 5 yes 0.11 12 4 × 0 1800+ 20 40 16 9 no 0.10 12 4 × 01800+ 23 40 21 12  no 0.12 12 4 × 0 1800+ 21 40 17 P-514¹ no 0.12 12 4 ×0 1800+ 22 40 12 P-208² n.a. 0.10 4 × 0 80 FC-845³ no 0.10

[0099] The following examples demonstrate the usefulness of the novelpolymers as soil-release, anti soil-redeposition and anti dry-soilingagents on textiles.

EXAMPLE 15

[0100] Application:

[0101] A 20×35 cm piece of fabric is treated with a pad-bath containingthe following:

[0102] 5.4 g/l fluorine of the fluorochemical copolymer solution ofexample 1;

[0103] 40 g/l melamine-formaldehyde cellulose crosslinker,

[0104] 12 g/l magnesium chloride as catalyst, and 1 g/l acetic acid.

[0105] The pick-up is adjusted to 100% by weight of fabric. The cloth isstretched across a nail-frame and dried at 110° C. for 10 minutes in anoven; then subsequently cured at 150° C. for 5 minutes.

[0106] Stain Release Test:

[0107] The test measures the release of stains after a household wash:2-3 cm diameter staining material is applied to the fabric and isremoved after 30 minutes with cotton swabs. After 20-24 hours the fabricis washed once at 60° C. and the soil release effect evaluated(=original); the fabric is then washed five or ten times respectivelyand the soiling test is repeated (=5×60° C. or 10×60° C.). Thesoil-release effect is judged after drying and ironing according to theSoil-Release Standard (DMRC of AATCC). In the example the values givenare the average of 14 common stains. Higher values denote betterperformance.

[0108] Wet-Soiling:

[0109] This test measures the degree of graying during washing incomparison with untreated fabric. Soiling standard: 0.3 g Diphasol 7568surfactant are dissolved in 1 l hot water, 0.5 g carbon black are addedand the mixture brought to a short boil. Then 100 ml of this mixture areadded to 1 l water and 5×5 cm fabric swatches are immersed for 20minutes at 80° C. for cotton, and cotton/polyester, and at 40° C. forpolyester.

[0110] After a quick rinse the soiled samples are washed with 3 g/l washpowder at 60° C. for cotton and cotton/polyester, and at 40° C. forpolyester.

[0111] Evaluation is after drying, visually in comparison with untreatedfabric. Higher values denote better performance.

[0112] Dry-Soiling:

[0113] In a 30 cm long cylinder with 15 cm diameter equal parts of 5×5cm fabric swatches, standard dry soil and 5 mm diameter metal balls aretumbled for 20 minutes: then tumbled with new balls and without soil foranother 5 minutes. Evaluation is visual using an AATCC gray scale, withrating from 1 (worst) to 5 (best, no change).

[0114] Initial Oil Repellency is determined according to AATCC 118;Water Repellency is determined according to AATCC 22.

[0115] The test fabrics are 100% cotton tablecloth (=CO woven) and 65/35cotton/polyester work ware(=CO/PE woven); 100% cotton knit (=CO knit)and 65/35 cotton/polyester knit (=CO/PE knit); the tested compound is ofExample 1; the commercial Soil-Release agent Scotchguard FC-248 (3MCompany) is used as a standard for comparison. TABLE Results of SoilRelease Test 60° C. washes, FC-248 Cpd. of Ex. 1 control Fabric none 510 none 5 10 1 CO weave 3.8 3.5 3.5 3.8 3.7 3.6 2.4 CO knit 4.5 4.1 3.94.4 3.8 3.7 2.4 CO/PE weave 4.3 5.0 3.8 3.9 3.2 3.4 2.4 CO/PE knit 4.13.4 3.3 3.9 3.6 3.1 2.2

[0116] TABLE Results of Oil and Water Repellency Tests FC-248 Cpd. ofEx. 1 TEST Water Water Drop Water Water Drop 60° C. washes, spray oilTest spray oil Test fabric 1 1 1 5 10 1 1 1 5 10 CO weave 50 5 8 0 0 506 4 5 4 CO knit 70 5 4 0 0 80 6 4 0 0 CO/PE weave 50 6 5 5 5 50 6 3 4 3CO/PE knit 50 6 8 7 5 70 6 3 4 3

[0117] TABLE Results of Wet Soil Redeposition and of Dry-Soiling Test.wet soil redeposition dry soiling Compound Cpd. of Cpd. of Fabric FC-248Ex. 1 Cont. FC-248 Ex. 1 Cont. CO weave 4.5 4 3 3 4 1.5 CO knit 3.5 3.52.5 3.5 4 1.5 CO/PE weave 4 3.5 4 3 3.5 1 CO/PE knit 3.5 3 2 3 3.5 1

What is claimed is:
 1. A copolymer of a) 45-90% by weight of aperfluoroalkyl-substituted (meth)acrylate or (meth)acrylamide, b) 5-30%by weight of a secondary or tertiary amino or quaternary ammoniumgroup-containing (meth)acrylate or (meth)acrylamide, c) 1-20% by weightof vinylidene chloride, and, optionally, d) 0-10% by weight of acopolymerizable nonfluorinated vinyl monomer.
 2. A copolymer accordingto claim 1, comprising monomers copolymerized in the followingpercentages by weight, relative to the total weight of the copolymer a)45-90% by weight of a monomer of formula R_(F)—W—X—C(═O)—C(R₁)═CH₂  (1), wherein R_(F) is a straight or branched-chain perfluoroalkylgroup containing 4 to 20 carbon atoms, R₁ is H or CH₃, X is O, S orN(R₂), wherein R₂ is H or an alkyl group with 1 to 4 carbon atoms, W isalkylene with 1 to 15 carbon atoms, hydroxyalkylene with 3 to 15 carbonatoms, -(C_(n)H_(2n))(O C_(m)H_(2m))_(q)-, —SO₂NR₂-(C_(n)H_(2n))- or—CONR₂-(C_(n)H_(2n))-, wherein n is 1 to 12, m is 2 to 4, q is 1 to 10and R₂ is as defined above; b) 5-30% by weight of a monomer of formula(R₂)₂N-(CH₂)_(k)—X₁—C(═O)—C(R₁)═CH₂   (2), in which the nitrogen atom ispartially or completely quaternized or in the form of a salt and X₁ is Oor N(R₂) and wherein R₁ and R₂ are defined as above, each R₂ is the sameor different, and k is 2 to 4; c) 1-20% by weight of vinylidenechloride, and, optionally, d) 0-10% by weight of a copolymerizablenonfluorinated vinyl monomer.
 3. A copolymer according to claim 1,wherein d) is zero.
 4. A copolymer according to claim 2, in which themonomers are copolymerized in the following percentages by weight,relative to the total weight of the copolymers: a), 70-85% by weight;b), 3-12% by weight; c), 10-20% by weight, and d), zero.
 5. A copolymeraccording to claim 2, wherein R_(F) is a straight chain perfluoroalkylgroup with 6-16 carbon atoms, X and X₁ are oxygen and W is an alkylenewith 1 to 12 carbon atoms.
 6. A copolymer according to claim 5, whereinR₁ is hydrogen and W is —CH₂CH₂—.
 7. A copolymer according to claim 2,wherein R_(F) is a straight chain perfluoroalkyl group with 6-16 carbonatoms, X is N(R₂), X₁ is oxygen and W is —SO₂NR₂-(C_(n)H_(2n))-.
 8. Acopolymer according to claim 2, wherein R_(F) comprises a mixture ofstraight chain perfluoroalkyl groups with 6-16 carbon atoms.
 9. Acopolymer according to claim 2, in which the monomer of the formula (2)is selected from the group consisting of N,N-dimethylaminoethyl(meth)acrylate; N,N-diethylaminoethyl (meth)acrylate;N,N-dimethylaminopropyl methacrylamide and N-tert. butylaminoethylmethacrylate and their salts.
 10. A copolymer according to claim 2, inwhich co-monomer (d) is selected from the group consisting of acrylates,methacrylates and styrene.
 11. A copolymer according to claim 2, inwhich co-monomer (d) is selected from the group consisting of methylmethacrylate, N-methylol acrylamide, 2-hydroxyethyl methacrylate,acrylic acid, glycidyl methacrylate and acrylonitrile.
 12. A process forthe preparation of copolymer according to claim 1, comprising reactinga) 45-90% by weight of a perfluoroalkyl-substituted (meth)acrylate or(meth)acrylamide, b) 5-30% by weight of a secondary or tertiary amino orquaternary ammonium group-containing (meth)acrylate or methacrylamide,c) 1-20% by weight of vinylidene chloride, and, optionally, d) 0-10% byweight of a copolymerizable nonfluorinated vinyl monomer, and,optionally, a chain-transfer agent, in the presence of a free radicalinitiator.
 13. A method to impart oil and grease resistance to paper,which comprises incorporating an amount of a copolymer according toclaim 1 that is effective to impart oil and grease resistance into thepaper.
 14. A method according to claim 13, wherein the copolymer isapplied to dry paper through a coating process in a size-press or byaddition of the copolymer to an aqueous pulp.
 15. A method according toclaim 13, wherein 0.02 to 1% by weight of the copolymer is applied,based on the dry weight of the paper or pulp.
 16. A method to impartsoil-release and anti-soiling characteristics to a textile material,which comprises treating the textile material with an amount of acopolymer according to claim 1 that is effective to impart soil-releaseand anti-soiling characteristics thereto.
 17. A method according toclaim 16, wherein the textile material is treated with 0.02 to 1% byweight of the copolymer, based on the weight of the dry textilematerial.
 18. Oil and grease resistant paper or pulp which comprises0.02 to 1% by weight of a copolymer according to claim
 1. 19. Textilematerial, which comprises 0.02 to 1% by weight of a copolymer accordingto claim
 1. 20. A textile material according to claim 19, which isselected from the group consisting of cellulosics, polyamides,polyesters and polyolefins and blends thereof.
 21. A textile materialaccording to claim 20, which is selected from the group consisting ofcotton, nylon, wool, silk and polyester-cotton blends.